- COMPOSITES, METHODS AND USES THEREOF
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The present invention relates, in general terms, to methods of catalysing a reaction, including the steps of contacting a chemical entity comprising a sulphide moiety with a composite and an oxidant. The composite acts as a heterogeneous catalyst to oxidise the sulphide moiety. The present invention also relates to composites, methods of synthesising the composites and its use as a catalyst thereof.
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Page/Page column 26; 32
(2021/06/04)
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- Cobalt Single-Atom-Intercalated Molybdenum Disulfide for Sulfide Oxidation with Exceptional Chemoselectivity
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The identification of chemoselective oxidation process en route to fine chemicals and specialty chemicals is a long-standing pursuit in chemical synthesis. A vertically structured, cobalt single atom-intercalated molybdenum disulfide catalyst (Co1-in-MoS2) is developed for the chemoselective transformation of sulfides to sulfone derivatives. The single-atom encapsulation alters the electron structure of catalyst owing to confinement effect and strong metal–substrate interaction, thus enhancing adsorption of sulfides and chemoselective oxidation at the edge sites of MoS2 to achieve excellent yields of up to 99% for 34 examples. The synthetic scopes can be extended to sulfide-bearing alkenes, alkynes, aldehydes, ketones, boronic esters, and amines derivatives as a toolbox for the synthesis of high-value, multifunctional sulfones and late-stage functionalization of pharmaceuticals, e.g., Tamiflu. The synthetic utility of cobalt single atom-intercalated MoS2, together with its reusability, scalability, and simplified purification process, renders it promising for industrial productions.
- Chen, Zhongxin,Liu, Cuibo,Liu, Jia,Li, Jing,Xi, Shibo,Chi, Xiao,Xu, Haisen,Park, In-Hyeok,Peng, Xinwen,Li, Xing,Yu, Wei,Liu, Xiaowang,Zhong, Linxin,Leng, Kai,Huang, Wei,Koh, Ming Joo,Loh, Kian Ping
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- Direct Decarboxylative Allylation and Arylation of Aliphatic Carboxylic Acids Using Flavin-Mediated Photoredox Catalysis
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We describe herein a direct decarboxylative allylation of aliphatic carboxylic acids with allylsulfones using visible light and riboflavin tetraacetate (RFTA) as photocatalyst. The reaction proceeds at room temperature tolerating a wide range of functiona
- Ramirez, Nieves P.,Lana-Villarreal, Teresa,Gonzalez-Gomez, Jose C.
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supporting information
p. 1539 - 1550
(2019/08/07)
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- Catalyst-Free Deaminative Functionalizations of Primary Amines by Photoinduced Single-Electron Transfer
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The use of pyridinium-activated primary amines as photoactive functional groups for deaminative generation of alkyl radicals under catalyst-free conditions is described. By taking advantage of the visible light absorptivity of electron donor–acceptor complexes between Katritzky pyridinium salts and either Hantzsch ester or Et3N, photoinduced single-electron transfer could be initiated in the absence of a photocatalyst. This general reactivity platform has been applied to deaminative alkylation (Giese), allylation, vinylation, alkynylation, thioetherification, and hydrodeamination reactions. The mild conditions are amenable to a diverse range of primary and secondary alkyl pyridiniums and demonstrate broad functional group tolerance.
- Wu, Jingjing,Grant, Phillip S.,Li, Xiabing,Noble, Adam,Aggarwal, Varinder K.
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supporting information
p. 5697 - 5701
(2019/03/21)
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- Sulfinate-Organocatalyzed (3+2) Annulation Reaction of Propargyl or Allenyl Sulfones with Activated Imines
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An operationally simple methodology for the synthesis of 4-sulfonyl-3-pyrrolines is described using a propargylic sulfone and N-sulfonyl imines as substrates. This annulation process is initiated by an arenesulfinate organocatalyst, which allows a smooth isomerization of the alkynyl precursor into the corresponding allene, followed by the generation of a highly reactive allyl sulfone anion. An asymmetric version involving an unprecedented enantiopure sulfinate–ammonium cooperative ion pair (PhSO2– R4N+*) was investigated. A proof-of-concept, with enantiomeric excesses of up to 41 %, was obtained according to a preliminary screening of commercially available chiral phase-transfer catalysts.
- Martzel, Thomas,Lohier, Jean-Fran?ois,Gaumont, Annie-Claude,Brière, Jean-Fran?ois,Perrio, Stéphane
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supporting information
p. 5069 - 5073
(2018/09/14)
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- Aryl Ketone Catalyzed Radical Allylation of C(sp3)-H Bonds under Photoirradiation
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The catalytic introduction of an allyl group at nonacidic C(sp3)-H bonds was achieved under photoirradiation, in which 1,2-bis(phenylsulfonyl)-2-propene acts as an allyl source and 5,7,12,14-pentacenetetrone (PT) works as a C-H bond-cleaving catalyst. A variety of substances, including alkanes, carbamates, ethers, sulfides, and alcohols, were chemoselectively allylated in a single step under neutral conditions. The present transformation is catalyzed solely by an organic molecule, PT, and proceeds smoothly even under visible light irradiation (425 nm) in the case of alkanes as a starting substance.
- Kamijo, Shin,Kamijo, Kaori,Maruoka, Kiyotaka,Murafuji, Toshihiro
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supporting information
p. 6516 - 6519
(2016/12/23)
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- Catalyst-controlled divergence in cycloisomerisation reactions of N-propargyl-N-vinyl sulfonamides: Gold-catalysed synthesis of 2-sulfonylmethyl pyrroles and dihydropyridines
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Gold-catalysed, divergent synthesis of 2-sulfonylmethyl pyrroles and dihydropyridines from N-propargyl-N-vinyl sulfonamides has been achieved. Echavarren's gold(i) catalyst promoted the formation of pyrrole derivatives whereas the combination of PPh3AuCl and AgSbF6 afforded dihydropyridines. The aza-enyne precursors for the cycloisomerisation reaction were prepared by a base-mediated formal vinylic substitution reaction of 2-bromoallyl sulfones.
- Undeela, Sridhar,Thadkapally, Srinivas,Nanubolu, Jagadeesh Babu,Singarapu, Kiran Kumar,Menon, Rajeev S.
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supporting information
p. 13748 - 13751
(2015/09/07)
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- Base-Mediated Cyclocondensation of Salicylaldehydes and 2-Bromoallyl Sulfones for the Synthesis of 3-Sulfonylchromene Derivatives and Their Regioselective Friedel-Crafts Heteroarylation Reactions
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Cesium carbonate-mediated reaction of 2-hydroxybenzaldehydes and 2-bromoallyl sulfones afforded 2H- and 4H-chromenol derivatives endowed with a 3-arylsulfonyl group. 2-Bromoallyl sulfones functioned as synthetic equivalents of allenyl sulfones under these conditions. The 2H- and 4H-chromenol derivatives underwent regioselective Friedel-Crafts reactions with heteroarenes in the presence of p-toluenesulfonic acid to afford 4-heteroaryl-4H-chromene derivatives in excellent yields.
- Kumar, Anand,Thadkapally, Srinivas,Menon, Rajeev S.
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p. 11048 - 11056
(2015/11/18)
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- A regio- and diastereoselective platinum-catalyzed tandem [2+1]/[3+2] cycloaddition sequence
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Platinum complexes bearing phosphinous acids have efficiently promoted a tandem intermolecular sequence of [2+1]/[3+2] cycloaddition reactions. This process gave access to novel tricyclic systems and the cascade reactions were regio- and diastereoselective (see scheme; Cy=cyclohexyl). The [3+2] cycloaddition reaction was investigated further and two different alkyne partners were used. Copyright
- Achard, Thierry,Lepronier, Aymeric,Gimbert, Yves,Clavier, Herve,Giordano, Laurent,Tenaglia, Alphonse,Buono, Gerard
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supporting information; experimental part
p. 3552 - 3556
(2011/06/09)
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- Reduction of propargylic sulfones to (Z)-allylic sulfones using zinc and ammonium chloride
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Propargylic sulfones can be cis-hydrogenated using commercial zinc powder and ammonium chloride in THF-water at room temperature, the major products being the corresponding (Z)-allylic sulfones. Other reducible groups (alkene, benzyloxy) are not affected. Allenylsulfones are implicated in one of the possible reaction pathways.
- Sheldrake, Helen M.,Wallace, Timothy W.
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p. 4407 - 4411
(2008/02/03)
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- Selective oxidation of sulfides to sulfoxides and sulfones at room temperature using H2O2 and a Mo(VI) salt as catalyst
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Selective oxidation of sulfides to sulfoxides and sulfones is achieved by H2O2 using MoO2Cl2 as the catalyst. Various substituted sulfides having functional groups such as methyl, methoxy, bromo, nitro, alkene, alkyne, alcohol, ester, aldehyde and remarkably an oxime are successfully and selectively oxidized without affecting the sensitive functionalities.
- Jeyakumar, Kandasamy,Chand, Dillip Kumar
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p. 4573 - 4576
(2007/10/03)
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- Stannylated allylsulfones as versatile new building blocks
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Propargylic sulfones undergo regioselective hydrostannation in the presence of Mo(CO)3(CNt-Bu)3(MoBl3), giving rise to stannylated allyl sulfones. These are interesting building blocks, because in the first step the vinyls
- Kazmaier, Uli,Wesquet, Alexander
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p. 1271 - 1274
(2007/10/03)
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- Intramolecular [4+3] cycloadditions. Towards a synthesis of widdrol
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Certain substituted alkoxyallylic sulfones were alkylated and treated with Lewis acids to produce vinylthionium ions that underwent intramolecular [4+3] cycloaddition reactions with a tethered furan. Manipulation of the cycloadduct led to the synthesis of widdrol. Other attempts to prepare the cycloadducts were made, but none were exceptionally better than the route using vinylthionium ions as intermediates. Interesting aspects of the alkylation chemistry of phenylthio-substituted alkoxyallylic sulfones are detailed as well.
- Harmata, Michael,Kahraman, Mehmet,Adenu, Gilbert,Barnes, Charles L.
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p. 583 - 618
(2007/10/03)
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- Improved synthesis of 2,3-dibromo-1-(phenylsulfonyl)-1-propene (DBP)
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A convenient preparation of 2,3-dibromo-1-(phenylsulfonyl)-1-propene (DBP, 1) is available through the one-pot propargylation and oxidation of thiophenol to give the propargyl sulfone 11, which is isomerized and brominated in another one-pot reaction. The
- VanZanten, Aaron,Mullaugh, Katherine,Harrington, Ryan,Kiefer, Adam,Carlson, David,Mastarone, Dan,Lipchik, Corey,Murphree, S. Shaun
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p. 2611 - 2613
(2007/10/03)
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- Chromium(VI) oxide catalyzed oxidation of sulfides to sulfones with periodic acid
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A highly efficient and selective oxidation of sulfides to sulfones with periodic acid catalyzed by CrO3 is described. A variety of electron-rich and electron-deficient sulfides were oxidized to sulfones with 2 mol% CrO3 in acetonitrile at room temperature in excellent yields. Sulfides with other readily oxidized functional groups were selectively oxidized to sulfones in high yields with 10 mol% CrO3 in ethyl acetate/acetonitrile at -35 °C.
- Xu, Liang,Cheng, Jie,Trudell, Mark L.
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p. 5388 - 5391
(2007/10/03)
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- One-pot synthesis of aryl sulfones from alcohols
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A one-pot synthesis of aryl sulfones from primary alcohols is described. Alcohols were treated with N-bromosuccinimide and triphenylphosphine, followed by addition of sodium arenesulfinate with a catalytic amount of tetrabutylammonium iodide to afford the aryl sulfones in good to high yields.
- Murakami, Teiichi,Furusawa, Kiyotaka
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p. 479 - 482
(2007/10/03)
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- Selective oxidation of allylic sulfides by hydrogen peroxide with the trirutile-type solid oxide catalyst LiNbMoO6
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Chemoselective sulfur oxidation of allylic sulfides containing double bonds of high electron density due to multiple alkyl substituents or extended conjugation was developed using the composite metal oxide catalyst, LiNbMoO6, without any epoxidation of the electron-rich double bond(s). Selective oxidation to either the corresponding sulfoxides or the sulfones was realized by controlling the stoichiometry of the quantitative oxidant, H202. This new oxidant system had general applicability for chemoselective oxidation of various allylic, benzylic, or propargylic sulfides containing unsaturated carbon-carbon bonds with different electron properties. Various functional groups including hydroxy, formyl, and ethers of THP or TBDMS are compatible under this mild oxidation reaction condition.
- Choi, Soojin,Yang, Jae-Deuk,Ji, Minkoo,Choi, Hojin,Kee, Minyong,Ahn, Kwang-Hyun,Byeon, Song-Ho,Baik, Woonphil,Koo, Sangho
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p. 8192 - 8198
(2007/10/03)
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- Homolytic Displacement at Carbon. Part 3. First Example of α-Attack on the Allenyl- and Prop-2-ynyl-cobaloximes
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Allenylcobaloxime reacts with substituted benzenesulphonyl chlorides in an inert atmosphere under irradiation with tungsten lamps to give good yields of allenyl sulphones.However, the same reactions carried out in Srinivasan's photoreactor using a 400 W medium-pressure mercury lamp or under thermal conditions give exclusively prop-2-ynyl sulphones, by regiospecific rearrangement, in good yields.The corresponding reactions of (3,3-disubstituted allenyl) cobaloximes afford 1,1-disubstituted prop-2-ynyl sulphones irrespective of the conditions used.Similarly, prop-2-ynyl sulphones are formed exclusively in the reactions of prop-2-ynylcobaloxime with organosulphonyl chlorides under thermal and photochemical conditions.The reactions are believed to take place through a chain mechanism in which cobaloxime(II), present adventitiously or formed by partial homolysis of the substrate cobaloxime, abstrscts a chlorine atom from the organosulphonyl chloride to give the organosulphonyl radical RSO2.Depending upon the reaction conditions and the nature of cobaloxime, RSO2 attacks the α- or the γ-carbon atom of the axial organic group of the cobaloxime, thereby displacing cobaloxime(II) and giving the observed organic product.
- Gupta, B. Dass,Roy, Sujit
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p. 1377 - 1384
(2007/10/02)
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- HYDRATION OF 1- AND 3-ARYLSULFONYL-1-PROPYNES AND ARYLSULFONYLALLENES
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The reactions of isomeric 1- and 3-arylsulfonyl-1-propynes and arylsulfonylallenes with primary aromatic amines in organic solvent-water system lead to arylsulfonyl-2-propanones.Unstable addition products (enamines) are formed in the reaction and then undergo hydration and are transformed into the ketones.
- Mikhailova, V. N.,Bulat, A. D.,Yurevich, V. P.,Ezhova, L. A.
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p. 1756 - 1759
(2007/10/02)
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- Studies on the Addition of Allyl Oxides to Sulfonylallenes. Preparation of Highly Substituted Allyl Vinyl Ethers for Carbanionic Claisen Rearrangements
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Thirty-five allyl vinyl ethers bearing an arylsulfonyl anion-stabilizing group have been prepared by addition of allylic alkoxides to (arylsulfonyl)allenes.The allyl vinyl ethers are produced as either β,γ-unsaturated or α,β-unsaturated sulfones depending upon the substitution pattern of the allene and the reaction conditions.A wide variety of substitution patterns are available by using this method.Factors that control the position and stereochemistry of the vinyl ether double bond are discussed.
- Denmark, Scott E.,Harmata, Michael A.,White, Kathleen S.
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p. 4031 - 4042
(2007/10/02)
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- HOMOLYTIC DISPLACEMENT AT CARBON: FIRST EXAMPLE OF α-ATTACK IN THE ALLENYL AND PROPARGYL COBALOXIMES
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The reactions of allenyl and propalgyl cobaloximes with organosulphonyl chlorides under anaerobic and photochemical conditions form sulphones by a novel homolytic attack at the α carbon to the metal.
- Gupta, B.D.,Roy, Sujit
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p. 4905 - 4908
(2007/10/02)
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- Mass Spectral Rearrangements of 3-Arylsulphonyl-2-arylthiopropenes and N-(4'-Arylsulphonyl-2'-butynyl)-N-(4"-arylthio-2"-butynyl)anilines
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Under electron impact the title compounds undergo skeletal rearrangement in the addition to the anticipated modes of cleavage.The 3-arylsulphonyl-2-arylthiopropenes readily eliminate sulphur dioxide.Other modes of fragmentation include rearrangement to a
- Glaspy, P. E.,Hancock, R. A.,Thyagarajan, B. S.
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p. 281 - 287
(2007/10/02)
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